Alkyl benzene sulfonyl urea photostabilizers and UV-absorbers

ABSTRACT

Polymers containing one or more novel photoactive moieties, sunscreen compositions including a mixture of a photoactive compound and a polymer containing one or more photoactive moieties are described herein. 
     Polymer of formula (I): 
                         
wherein the variables are as claimed.
 
     Also disclosed are methods for stabilizing a sunscreen composition, methods of filtering out ultra-violet light from a substrate by the addition of one or more of the foregoing polymers, methods accepting the triplet excited state energy with one or more of the foregoing polymer, and methods of increasing the UV-A Protective Value are described herein.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional of U.S. patent application Ser. No. 11/491,205,which is a continuation-in-part of U.S. patent application Ser. No.11/123,925, filed May 6, 2005 and issued Jun. 9, 2009, which is acontinuation-in-part of U.S. patent application Ser. No. 10/385,833,filed Mar. 11, 2003, and issued Nov. 8, 2005 as U.S. Pat. No. 6,962,692,which is a continuation-in-part of U.S. patent application Ser. No.10/302,423, filed Nov. 22, 2002 and issued Mar. 25, 2004 as U.S. Pat.No. 6,800,274, the disclosures of which are hereby incorporated hereinby reference.

BACKGROUND

1. Field of the Technology

The invention relates to compounds which absorb ultraviolet (UV) light,sunscreen compositions of these compounds, methods of protecting humanskin from UV radiation, methods of photostabilzing a dibenzoylmethanederivative, and methods of quenching triplet excited state energy. Moreparticularly, the invention relates to novel polymers terminated withα-cyano acrylates, acrylamides, and/or thioacrylates.

2. Brief Description of Related Technology

It is well known that UV radiation having a wavelength from about 280 nmor 290 nm to about 320 nm (UV-B) is harmful to human skin, causing burnsthat are detrimental to the development of a good sun tan. UV-Aradiation (about 320 nm to about 400 nm), while producing tanning of theskin, also can cause damage, particularly to very lightly colored orsensitive skin, leading to reduction of skin elasticity and wrinklesTherefore, a sunscreen composition for use on human skin preferablyincludes both a UV-A and a UV-B filter to prevent most of the sunlightwithin the full range of about 280 nm to about 400 nm from damaginghuman skin.

Ultraviolet radiation from the sun or artificial sources can also causeharm to coatings containing photoactive substances, such as photoactivepigments and dyes, by breaking down chemical bonds in the structure of acomponent such as a polymer, a pigment, or a dye. This photodegradationcan lead to yellowing, color fading, loss of gloss, and loss of physicaland protective properties of a coating. Photodegradation can take placein several steps which include one or more components of a coatingabsorbing UV radiation. The absorbed radiation can excite the absorbingmolecules and raise them to a higher energy level, which can be veryreactive. If the molecule cannot be relaxed, bond cleavage and theformation of free radicals will occur. These free radicals can attackone or more color molecules and/or a polymer backbone and form more freeradicals. UV-A and UV-B filters can also be used to absorb UV radiationto protect a pigmented coating.

The UV-B filters that are most widely used in the U.S. in commercialsunscreen compositions are paramethoxycinnamic acid esters, such as2-ethylhexyl paramethoxycinnamate, commonly referred to as octylmethoxycinnamate or PARSOL MCX, octyl salicylate, and oxybenzone.

The organic UV-A filters most commonly used in commercial sunscreencompositions are the dibenzoylmethane derivatives, particularly 4-(1,1dimethylethyl)-4′ methoxydibenzoylmethane (also called avobenzone, soldunder the brand name PARSOL 1789). Other dibenzoylmethane derivativesdescribed as UV-A filters are disclosed in U.S. Pat. Nos. 4,489,057,4,387,089 and 4,562,067, the disclosures of which are herebyincorporated herein by reference. It is also well known that the abovedescribed UV-A filters, particularly the dibenzoylmethane derivatives,can suffer from rapid photochemical degradation, when used alone or whencombined with the above described most commercially used UV-B filters.

Typically, the above described UV-B filters are combined with the abovedescribed UV-A filters in a solution with other lipophilic or oilyingredients. This solution of oily ingredients, known to formulators ofcosmetic products including sunscreens as the “oil phase,” is typically,but not necessarily, dispersed with the help of emulsifiers andstabilizers into an aqueous solution composed primarily of water, tomake an emulsion which becomes a final cream or lotion form of asunscreen composition.

The performance of a photoactive compound or a combination ofphotoactive compounds in a sunscreen composition has been extremelydifficult to predict based on the levels of photoactive compounds in theformulation, particularly when the formulation includes one or morephotoactive compounds that suffer from relatively rapidphotodegradation, such as avobenzone. Because of this, each formulationhas required expensive laboratory testing to determine the UVabsorbance, as a function of time (quantity) of exposure of theformulation to UV radiation. Moreover, a particularly difficult problemis presented when one photoactive compound in a sunscreen compositionacts to increase the rate of photodegradation of another photoactivecompound in the composition. This can be accomplished in a number orways, including a bimolecular reaction between two photoactive compoundsand a lowering of the threshold energy need to raise a photoactivecompound to its excited state. For example, when avobenzone is combinedwith octyl methoxycinnamate a bimolecular pathway leads to the rapidphotodegradation of both the dibenzoylmethane derivative and the octylmethoxycinnamate.

Methods and compositions for stabilizing photoactive compounds, such asdibenzoylmethane derivatives with the use of diesters and/or polyestersof naphthalene dicarboxylic acid are described in U.S. Pat. Nos.5,993,789, and 6,284,916, the disclosures of which are herebyincorporated herein by reference. Other methods of stabilizing adibenzoylmethane derivative include the addition of a α-cyanoβ,β-diphenylacrylate compound to a sunscreen composition that includes adibenzoylmethane derivative. See, Deflandre et al, U.S. Pat. No.5,576,354 and Gonzenbach et al., U.S. Pat. No. 6,033,649.

SUMMARY

One aspect of the compounds, compositions, and methods described hereinis a polymeric compound terminated with α-cyano acrylates, acrylamides,and/or thioacrylates, such as a compound of formula (I) as describedbelow.

Another aspect of the compounds, compositions, and methods describedherein is a sunscreen composition including a photoactive compound and apolymeric compound terminated with α-cyano acrylates, acrylamides,and/or thioacrylates, such as a compound of formula (I) as describedbelow.

Another aspect of the compounds, compositions, and methods describedherein is a method of protecting a surface from ultra-violet lightincluding applying a polymeric compound terminated with α-cyanoacrylates, acrylamides, and/or thioacrylates, such as a compound offormula (I) as described below, or a composition containing the same tothe surface.

Yet another aspect of the compounds, compositions, and methods describedherein is a method of photostabilizing a dibenzoylmethane derivative byadding a polymeric compound terminated with α-cyano acrylates,acrylamides, and/or thioacrylates, such as a compound of formula (I) asdescribed below, to a composition containing a dibenzoylmethanederivative.

Yet another aspect of the compounds, compositions, and methods describedherein is a method of quenching triplet excited state energy from atriplet-excited photoactive compound in a sunscreen composition byadding to the composition a polymeric compound terminated with α-cyanoacrylates, acrylamides, and/or thioacrylates, such as a compound offormula (I) as described below.

Still another aspect of the compounds, compositions, and methodsdescribed herein is methods of increasing or “boosting” the UV-Aprotective value of the compositions by adding to the composition apolymer terminated with a α-cyano acrylates, acrylamides, and/orthioacrylates, such as a compound of formula (I) as described below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the absorbance of Polymer Derivative 1 (an α-cyanoβ-p-methoxyphenyl β-napthyl acrylate terminated polymer) at aconcentration of 10.6 ppm and from a wavelength of 250 nm to 450 nm.

FIG. 2 is a graph of the absorbance of a sunscreen composition thatincludes 3% by weight of Polycrylene® and 3% by weight avobenzone beforeand after irradiation of 120 J/cm².

FIG. 3 is a graph of the absorbance of a sunscreen composition thatincludes 3% by weight of Polymer Derivative 1 (an α-cyanoβ-p-methoxyphenyl β-napthyl acrylate terminated polymer) and 3% byweight avobenzone before and after irradiation of 120 J/cm².

FIG. 4 is a graph of the absorbance of a sunscreen composition thatincludes 3% by weight of Polymer Derivative 1, 0.75% by weight TinosorbS, and 3% by weight avobenzone before and after irradiation of 120J/cm².

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Photostabilzing polymers having at least one α-cyano β-aryl acrylate oracrylate derivative, sunscreen compositions having a photostabilzingpolymer and one or more photoactive compound, such as a dibenzoylmethanederivative UV-A filter compound, are described herein. One aspect of thesunscreen compositions described herein are methods of photostabilizinga sunscreen composition including a dibenzoylmethane derivative, such as4-(1,1-dimethylethyl)-4′-methoxydibenzoylmethane (PARSOL®1789/Avobenzone), wherein one or more photoactive compounds present in asunscreen composition (e.g., Avobenzone) are made more photostable bythe addition of a polymer having at least one α-cyano β-aryl acrylate oracrylate derivative. Also disclosed herein are methods for filtering outultra-violet light from human skin including the step of applying apolymer having at least one α-cyano β-aryl acrylate or acrylatederivative to the skin. Also disclosed herein are methods for increasingor “boosting” the UV-A protective value of a sunscreen compositionincluding the step of applying a polymer having at least one α-cyanoβ-aryl acrylate or acrylate derivative to the skin.

A photoactive compound can be considered stable when, for example, after30 MED irradiation the photoactive compound has retained at least about90% of its original absorbance at a wavelength or a range of wavelengthsof interest (e.g., the wavelength at which or near a photoactivecompound has a peak absorbance, such as 350-370 nm for avobenzone).Likewise, a sunscreen composition can include a plurality of photoactivecompounds and a sunscreen composition, as a whole, can be consideredstable when, for example, after 30 MED irradiation the sunscreencomposition has retained at least about 90% of its original absorbanceat one or more wavelengths of interest (e.g., at or near the peakabsorbance wavelength of the primary photoactive compounds).

It has surprisingly been found that the addition of one or more of apolymer having at least one α-cyano β, β-diaryl acrylate or acrylatederivative increases the photostability of the sunscreen compositionand/or photounstable components present therein. Without intending to belimited to any particular mechanism of achieving this increase instability, it is believed that such compounds, such as the compounds offormula (I) described below, stabilize a photounstable component of asunscreen composition (e.g., a dibenzoylmethane derivative) by acceptingthe triplet excited state energy of a dibenzoylmethane derivative thathas reached an excited state as a result of the absorption ofultra-violet light. Once a dibenzoylmethane derivative is excited, it isprone to degrade according to a number of pathways; however, thedegradation of the dibenzoylmethane derivative can be substantiallyreduced or prevented when a polymer terminated with an α-cyano β,β-diaryl acrylate derivative, such as the compounds of formula (I)described below, is added to quench (accept) the triplet excited stateenergy present in an excited dibenzoylmethane molecule. Thus, in onepathway of degradation, a dibenzoylmethane derivative is excited to itstriplet state and the excited state triplet energy is released in a bondbreaking step, thereby preventing the dibenzoylmethane derivative fromfurther accepting ultra-violet radiation. A polymer terminated with anα-cyano β, β-diaryl acrylate derivative, such as the compounds offormula (I) described below, stabilizes a dibenzoylmethane derivative byaccepting the triplet state (excited state) energy of the exciteddibenzoylmethane derivative in such a way as to convert the exciteddibenzoylmethane derivative back to a ground state that is capable ofreaccepting ultra-violet radiation (energy transfer). Without intendingto be limited to any particular mechanism by which a such compounds areable to quench (accept the excited state energy) an excited photoactivecompound, it is believed that a polymer terminated with an α-cyano β,β-diaryl acrylate derivative, such as the compounds of formula (I)described below, accepts the excited state energy and dissipates theenergy kinetically in the form of rapid isomerizations. An example ofthis process is shown below:

wherein the compound designated A above is an acrylate polymer (Rrepresents the rest of the polyester compound formed from thecombination of neopentyl glycol and adipic acid (see Examples 1 and 2below), accepts the triplet excited state energy and forms a diradical(shown above as A*) at the α and β positions of the acrylate, whichconverts the double bond into a single bond and allows for free rotationabout the single bond. This rotation occurs rapidly and efficiently todissipate excited state energy accepted by the polymer terminated withan α-cyano β, β-diaryl acrylate derivative, such as the compounds offormula (I) described below.

A sunscreen composition disclosed herein can be combined into acosmetically acceptable carrier, optionally including emollients,stabilizers, emulsifiers, such as those known in the art, andcombinations thereof. These additives can be used in preparing anemulsion from an aqueous system and a mixture of a filter system thatincludes one or more photoactive compounds and a solvent system thatincludes one or more organic solvents. When made, preferably theemulsion is an oil-in-water emulsion, wherein the oil phase is primarilyformed from a mixture of the filter system and solvent system.

A typical sunscreen composition includes one or more photoactivecompounds, wherein a photoactive compound acts to absorb UV radiationand thereby protect the substrate (e.g., human skin) from the harmfuleffects of UV radiation. The absorption process causes a photoactivecompound to reach an excited state, wherein the excited state ischaracterized by the presence of excited energy (e.g., singlet energy ortriplet energy), as compared to the ground state of the photoactivecompound. Once a photoactive compound reaches an excited state thereexists a number of pathways by which the excited photoactive compoundcan dissipate its excess energy (e.g., triplet energy), however, many ofthose pathways adversely affect the ability of the photoactive compoundto further absorb UV radiation.

A photoactive compound is one that responds to light photoelectrically.In the compositions disclosed herein, a photoactive compound is one thatresponds to UV radiation photoelectrically. For example, photoactivecompounds that respond to UV radiation photoelectrically by rapidphotodegradation can benefit highly from the compositions and methodsdisclosed herein, even though the benefits of the compositions andmethods disclosed herein are not limited to such compounds.Photostability is a potential problem with all UV filters because theyare deliberately selected as UV absorbing molecules. In otherapplications, a photoactive compound may be a pigment or a dye (e.g., ahydrophobic dye).

UV filters include compounds selected from the following categories(with specific examples) including: p-aminobenzoic acid, its salts andits derivatives (ethyl, isobutyl, glyceryl esters;p-dimethylaminobenzoic acid); anthranilates (o-aminobenzoates; methyl,menthyl, phenyl, benzyl, phenylethyl, linalyl, terpinyl, andcyclohexenyl esters); salicylates (octyl, amyl, phenyl, benzyl, menthyl(homosalate), glyceryl, and dipropyleneglycol esters); cinnamic acidderivatives (menthyl and benzyl esters, alpha-phenyl cinnamonitrile;butyl cinnamoyl pyruvate); dihydroxycinnamic acid derivatives(umbelliferone, methylumbelliferone, methylaceto-umbelliferone); camphorderivatives (3-benzylidene, 4-methylbenzylidene, polyacrylamidomethylbenzylidene, benzalkonium methosulfate, benzylidene camphor sulfonicacid, and terephthalylidene dicamphor sulfonic acid); trihydroxycinnamicacid derivatives (esculetin, methylesculetin, daphnetin, and theglucosides, esculin and daphnin); hydrocarbons (diphenylbutadiene,stilbene); dibenzalacetone; benzalacetophenone; naphtholsulfonates(sodium salts of 2-naphthol-3,6-disulfonic and of2-naphthol-6,8-disulfonic acids); dihydroxy-naphthoic acid and itssalts; n- and p-hydroxydiphenyldisulfonates; coumarin derivatives(7-hydroxy, 7-methyl, 3-phenyl); diazoles (2-acetyl-3-bromoindazole,phenyl benzoxazole, methyl naphthoxazole, various aryl benzothiazoles);quinine salts (bisulfate, sulfate, chloride, oleate, and tannate);quinoline derivatives (8-hydroxyquinoline salts, 2-phenylquinoline);hydroxy- or methoxy-substituted benzophenones; uric acid derivatives;vilouric acid derivatives; tannic acid and its derivatives;hydroquinone; and benzophenones (oxybenzone, sulisobenzone,dioxybenzone, benzoresorcinol, 2,2′,4,4′-tetrahydroxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxybenzophenone, octabenzone,4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane, etocrylene,and 4-isopropyl-dibenzoylmethane).

Particularly useful are: 2-ethylhexyl p-methoxycinnamate, 4,4′-t-butylmethoxydibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, octyldimethylp-aminobenzoic acid, digalloyltrioleate,2,2-dihydroxy-4-methoxybenzophenone, ethyl4-[bis(hydroxypropyl)]aminobenzoate,2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexylsalicylate,glycerol p-aminobenzoate, 3,3,5-trimethylcyclohexylsalicylate,methylanthranilate, p-dimethylaminobenzoic acid or aminobenzoate,2-ethylhexyl p-dimethylaminobenzoate, 2-phenylbenzimidazole-5-sulfonicacid, 2-(p-dimethylaminophenyl-5-sulfoniobenzoxazoic acid, andcombinations thereof.

For a product marketed in the United States, preferredcosmetically-acceptable photoactive compounds and concentrations(reported as a percentage by weight of the total cosmetic sunscreencomposition) include: aminobenzoic acid (also called para-aminobenzoicacid and PABA; 15% or less), avobenzone (also called butyl methoxydibenzoylmethane; 3% or less), cinoxate (also called 2-ethoxyethylp-methoxycinnamate; 3% or less), dioxybenzone (also calledbenzophenone-8; 3% or less), homosalate (15% or less), menthylanthranilate (also called menthyl 2-aminobenzoate; 5% or less),octocrylene (also called 2-ethylhexyl-2-cyano-3,3 diphenylacrylate; 10%or less), octyl methoxycinnamate (7.5% or less), octyl salicylate (alsocalled 2-ethylhexyl salicylate; 5% or less), oxybenzone (also calledbenzophenone-3; 6% or less), padimate O (also called octyl dimethylPABA; 8% or less), phenylbenzimidazole sulfonic acid (water soluble; 4%or less), sulisobenzone (also called benzophenone-4; 10% or less),titanium dioxide (25% or less), trolamine salicylate (also calledtriethanolamine salicylate; 12% or less), and zinc oxide (25% or less).

Other preferred cosmetically-acceptable photoactive compounds andpreferred concentrations (percent by weight of the total cosmeticsunscreen composition) include diethanolamine methoxycinnamate (10% orless), ethyl-[bis(hydroxypropyl)]aminobenzoate (5% or less), glycerylaminobenzoate (3% or less), 4-isopropyl dibenzoylmethane (5% or less),4-methylbenzylidene camphor (6% or less), terephthalylidene dicamphorsulfonic acid (10% or less), and sulisobenzone (also calledbenzophenone-4, 10% or less).

For a product marketed in the European Union, preferredcosmetically-acceptable photoactive compounds and preferredconcentrations (reported as a percentage by weight of the total cosmeticsunscreen composition) include: PABA (5% or less), camphor benzalkoniummethosulfate (6% or less), homosalate (10% or less), benzophenone-3 (10%or less), phenylbenzimidazole sulfonic acid (8% or less, expressed asacid), terephthalidene dicamphor sulfonic acid (10% or less, expressedas acid), butyl methoxydibenzoylmethane (5% or less), benzylidenecamphor sulfonic acid (6% or less, expressed as acid), octocrylene (10%or less, expressed as acid), polyacrylamidomethyl benzylidene camphor(6% or less), ethylhexyl methoxycinnamate (10% or less), PEG-25 PABA(10% or less), isoamyl p-methoxycinnamate (10% or less), ethylhexyltriazone (5% or less), drometrizole trielloxane (15% or less),diethylhexyl butamido triazone (10% or less), 4-methylbenzylidenecamphor (4% or less), 3-benzylidene camphor (2% or less), ethylhexylsalicylate (5% or less), ethylhexyl dimethyl PABA (8% or less),benzophenone-4 (5%, expressed as acid), methylene bis-benztriazolyltetramethylbutylphenol (10% or less), disodium phenyl dibenzimidazoletetrasulfonate (10% or less, expressed as acid), bis-ethylhexyloxyphenolmethoxyphenol triazine (10% or less), methylene bisbenzotriazolyltetramethylbutylphenol (10% or less, also called TINOSORB M), andbisethylhexyloxyphenol methoxyphenyl triazine (10% or less, also calledTINOSORB S).

All of the above-described UV filters are commercially available. Forexample, suitable commercially-available organic UV filters areidentified by trade name and supplier in Table I below:

TABLE I CTFA Name Trade Name Supplier benzophenone-3 UVINULM-40 BASFChemical Co. benzophenone-4 UVINUL ® MS-40 BASF Chemical Co.benzophenone-8 SPECTRA-SORB ® UV-24 American CyanamidDEA-methoxycinnamate BERNEL HYDRO Bernel Chemical ethyldihydroxypropyl-PABA AMERSCREEN ® P Amerchol Corp. glyceryl PABA NIPAG.M.P.A. Nipa Labs. homosalate KEMESTER ® HMS Humko Chemical menthylanthranilate SUNAROME ® UV-A Felton Worldwide octocrylene UVINUL ® N-539BASF Chemical Co. octyl dimethyl PABA AMERSCOL Amerchol Corp. octylmethoxycinnamate PARSOL MCX Bernel Chemical PABA PABA National Starch2-phenylbenzimidazole-5- EUSOLEX ® 6300 EM Industries sulphonic acid TEAsalicylate SUNAROME ® W Felton Worldwide 2-(4-methylbenzildene)-EUSOLEX ® 6300 EM Industries camphor diethylamino hydroxybenzoylUVINUL ® A Plus BASF Chemical Co. hexyl benzoate benzophenone-1 UVINUL ®400 BASF Chemical Co. benzophenone-2 UVINUL ® D-50 BASF Chemical Co.benzophenone-6 UVINUL ® D-49 BASF Chemical Co. benzophenone-12 UVINUL ®408 BASF Chemical Co. 4-isopropyl dibenzoyl methane EUSOLEX 8020 EMIndustries disodium phenyl NEO HELIOPAN ® AP Symrise GmbH & Co.dibenzimidazole tetrasulfonate butyl methoxy dibenzoyl PARSOL ® 1789Givaudan Corp. methane etocrylene UVINUL ® N-35 BASF Chemical Co.methylene bisbenzotriazolyl TINOSORB ® M Ciba Specialtytetramethylbutylphenol Chemicals bisethylhexyloxyphenol TINOSORB ® SCiba Specialty methoxyphenyl triazine. Chemicals

The term “alkyl” as used herein refers to straight- and branched-chainhydrocarbon groups, preferably containing one to thirty carbon atoms.Examples of alkyl groups are C₁-C₄ alkyl groups. As used herein thedesignation C_(x)-C_(y), wherein x and y are integers, denotes a grouphaving from x to y carbon atoms, e.g., a C₁-C₄ alkyl group is an alkylgroup having one to four carbon atoms. Nonlimiting examples of alkylgroups include, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl(2-methylpropyl), t-butyl (1,1-dimethylethyl), and 3,3-dimethylpentane.

The term “cycloalkyl” as used herein refers to an aliphatic cyclichydrocarbon group, preferably containing three to eight carbon atoms.Nonlimiting examples of cycloalkyl groups include cyclopropyl,cyclobutyl, cyclopentyl, and cyclohexyl.

The term “alkenyl” as used herein includes both straight chained,branched, and cyclic hydrocarbon radicals that include at least onecarbon-carbon double bond, preferably, an alkenyl group contains betweentwo and thirty carbon atoms. Nonlimiting examples alkenyl groups includemethylene, ethylene, propylene, butylene, and isopropylene.

The terms “alkyne” and “alkynyl” as used herein include both straightand branched chained hydrocarbon radicals having at least onecarbon-carbon triple bond, preferably, an alkyne group contains betweentwo and thirty carbon atoms.

The term “polyether” as used herein refers to a group with at least twoethers present in a carbon chain. Nonlimiting examples of polyethersinclude 1-butoxy-2-methoxyethane, 1-butoxy-2-(2-methoxyethoxy)ethane,2-(2-methoxyethoxy)-1-(2-methylpentyloxy)propane, and1-(2-methylpentyloxy)-2-(2-pentyloxyethoxy)propane.

The terms “substituted alkyl,” “substituted cycloalkyl,” “substitutedalkenyl,” “substituted alkynyl,” and “substituted polyether” as usedherein refer to an alkyl, cycloalkyl, alkenyl, alkyne, or polyethergroup having one or more substituents. Substituents can include, but arenot limited to, alkyl, cycloalkyl, alkenyl, alkyne, polyether,substituted polyether, heteroaryl, heterocycloalkyl, aryl, substitutedaryl, substituted heteroaryl, substituted heterocycloalkyl, hydroxyl,ester, carboxy, cyano, amino, amido, sulfur, and halo. Preferredsubstituted alkyl groups have one to twenty carbon atoms, not includingcarbon atoms of the substituent group. Preferably, a substituted alkylgroup is mono- or di-substituted at one, two, or three carbon atoms. Thesubstituents can be bound to the same carbon or different carbon atoms.

The terms “ester” and “alkoxycarbonyl” as used herein refer to a groupof the general formula:

wherein R is an alkyl group, alkenyl group, alkyne group, cycloalkylgroup, polyether, aryl, substituted alkyl group, substituted alkenylgroup, substituted alkyne group, substituted cycloalkyl group,substituted aryl group, substituted heteroaryl, substitutedheterocycloalkyl, or substituted polyether group.

The term “aryl” as used herein refers to monocyclic, fused bicyclic, andfused tricyclic carbocyclic aromatic ring systems including, but notlimited to, phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl,biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl.

The term “heteroaryl” as used herein refers to monocyclic, fusedbicyclic, and fused tricyclic aromatic ring systems, wherein one tofour-ring atoms are selected from the group consisting of oxygen,nitrogen, and sulfur, and the remaining ring atoms are carbon, the ringsystem being joined to the remainder of the molecule by any of the ringatoms. Nonlimiting examples of heteroaryl groups include, but are notlimited to, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl,imidazolyl, thiazolyl, tetrazolyl, oxazolyl, isooxazolyl, thiadiazolyl,oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl,benzoxazolyl, benzimidazolyl, and benzothiazolyl.

The term “heterocycloalkyl” as used herein refers to an aliphatic,partially unsaturated or fully saturated, 3- to 14-membered ring system,including single rings of 3 to 8 atoms and bi- and tricyclic ringsystems. The heterocycloalkyl ring systems include one to fourheteroatoms independently selected from oxygen, nitrogen, and sulfur,wherein a nitrogen and sulfur heteroatom optionally can be oxidized anda nitrogen heteroatom optionally can be substituted. Representativeheterocycloalkyl groups include, but are not limited to, pyrrolidinyl,pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl,piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl,isothiazolidinyl, and tetrahydrofuryl.

The terms “substituted aryl,” “substituted heteroaryl,” and “substitutedheterocycloalkyl” as used herein refer to an aryl, heteroaryl, orheterocycloalkyl group substituted by a replacement of one, two, three,or four of the hydrogen atoms thereon with a substitute selected fromthe group consisting of alkyl, alkenyl, alkyne, substituted alkyl,substituted cycloalkyl, substituted alkenyl, substituted alkyne, ether,amino, aryl, heteroaryl, cycloalkyl, heterocycloalkyl, O(CH₂)₁₋₃N(R)₂,O(CH₂)₁₋₃CO₂H, hydroxyl, ester, carboxy, cyano, amino, amido, sulfur,and halo.

The term “amino” as used herein refers to an —NH₂ or —NH— group, whereineach hydrogen in each formula can be replaced with an alkyl, cycloalkyl,aryl, polyether, heteroaryl, heterocycloalkyl, substituted alkyl,substituted cycloalkyl, substituted aryl, substituted polyether,substituted heteroaryl, or substituted heterocycloalkyl group, i.e.,N(R)₂. In the case of —NH₂, the hydrogen atoms also can be replaced withsubstituents taken together to form a 5- or 6-membered aromatic ornon-aromatic ring, wherein one or two carbons of the ring optionally arereplaced with a heteroatom selected from the group consisting of sulfur,oxygen, and nitrogen. The ring also optionally can be substituted withan alkyl group. Examples of rings formed by substituents taken togetherwith the nitrogen atom include morpholinyl, phenylpiperazinyl,imidazolyl, pyrrolidinyl, (N-methyl)piperazinyl, and piperidinyl.

The term “amido” as used herein refers to a moiety of the generalformula:

wherein R¹ and R² are the same or different and selected from hydrogen,alkyl, alkenyl, alkyne, substituted alkyl, substituted alkenyl,substituted alkyne, aryl, alkenyl aryl, heteroaryl, and alkenylheteroaryl.

The term “cyano” as used herein refers to a —C≡N group, also designated—CN.

The term “halo” as used herein refers to fluorine, chlorine, bromine,and iodine.

The term “carboxy” or “carboxylate” as used herein refers to a moiety ofthe general formula:

wherein the hydrogen of the above moiety may optionally be substitutedwith a metal ion to form a carboxylate salt. Such metal ions include,but are not limited to, sodium, calcium, lithium, potassium, magnesium,and the like.

The term “hydroxyl” as used herein refers to an —OH group.

The term “alkoxy” as used herein refers to an —Oalkyl group, whereinalkyl represents a group as defined above.

The term “alkylcarbonyl as used herein refers to a moiety of the generalformula:

wherein alkyl is defined above.

The term “oxycarbonyl” as used herein refers to a moiety of formula—OC(O)R, where R is an alkyl, cycloalkyl, alkenyl, alkynyl, aryl,polyether, heteroaryl, heterocycloalkyl, substituted alkyl, substitutedcycloalkyl, substituted aryl, substituted polyether, substitutedheteroaryl, or substituted heterocycloalkyl group.

The term “thioether” as used herein refers to a moiety of formula —SR,wherein R is an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, polyether,heteroaryl, heterocycloalkyl, substituted alkyl, substituted cycloalkyl,substituted aryl, substituted polyether, substituted heteroaryl, orsubstituted heterocycloalkyl group.

The term “Polycrylene®” as used herein refers to a polymeric compoundwith the following Chemical Abstract Index name: Hexanedioic acid,polymer with 2,2-dimethyl-1,3-propanediol,3-[(2-cyano-1-oxo-3,3-diphenyl-2-propenyl)oxy]-2,2-dimethylpropyl2-octyldodecyl ester (CAS Reg. No. 862993-96-2). Polycrylene® andmethods for making the same are described in the commonly assigned U.S.Pat. Nos. 6,962,692 and 6,800,274, and is available from The C.P. HallCompany and affiliates thereof (Chicago, Ill.).

A sunscreen composition described herein can include a variety ofphotoactive compounds, including one or more UV-A photoactive compoundsand one or more UV-B photoactive compounds. Preferably, a sunscreencomposition includes a photoactive compound selected from the groupconsisting of p-aminobenzoic acid and salts and derivatives thereof;anthranilate and derivatives thereof; dibenzoylmethane and derivativesthereof; salicylate and derivatives thereof; cinnamic acid andderivatives thereof; dihydroxycinnamic acid and derivatives thereof;camphor and salts and derivatives thereof; trihydroxycinnamic acid andderivatives thereof; dibenzalacetone naphtholsulfonate and salts andderivatives thereof; benzalacetophenone naphtholsulfonate and salts andderivatives thereof; dihydroxy-naphthoic acid and salts thereof;o-hydroxydiphenyldisulfonate and salts and derivatives thereof;p-hydroxydiphenyldisulfonate and salts and derivatives thereof; coumarinand derivatives thereof; diazole derivatives; quinine derivatives andsalts thereof; quinoline derivatives; hydroxy-substituted benzophenonederivatives; methoxy-substituted benzophenone derivatives; uric acidderivatives; vilouric acid derivatives; tannic acid and derivativesthereof; hydroquinone; benzophenone derivatives; 1,3,5-triazinederivatives, phenyldibenzimidazole tetrasulfonate and salts andderivatives thereof; terephthalylidene dicamphor sulfonic acid and saltsand derivatives thereof; methylene bis-benzotriazolyltetramethylbutylphenol and salts and derivatives thereof;bis-ethylhexyloxyphenol methoxyphenyl triazine and salts and derivativesthereof; diethylamino hydroxybenzoyl hexyl benzoate and salts andderivatives thereof; and combinations of the foregoing.

It has been found that in a sunscreen composition described herein acompound of formula (I) is preferably combined with a photoactive agentselected from the group consisting ofbis-ethylethoxyphenol-methoxyphenol triazine, methylenebis-benzotriazolyl tetramethylbutyl phenol,diethylamino-hydroxybenzoyl-hexyl benzoate, disodiumphenyldibenzimidazoletetrasulfonate, octocrylene, di-octyl-naphthalate,and combinations thereof. More preferably, the composition includes aphotoactive compound that absorbs in the UV-A range (about 320 nm toabout 400 nm), such as those described below.

UV-A radiation (about 320 nm to about 400 nm) is recognized ascontributing to causing damage, particularly to very lightly-colored orsensitive skin. A sunscreen composition described herein preferablyincludes a UV-A photoactive compound. Preferably, a sunscreencomposition disclosed herein includes a dibenzoylmethane derivative UV-Aphotoactive compound. Preferred dibenzoylmethane derivatives include,2-methyldibenzoylmethane; 4-methyldibenzoylmethane;4-isopropyldibenzoylmethane; 4-tert-butyldibenzoylmethane;2,4-dimethyldibenzoylmethane; 2,5-dimethyldibenzoylmethane;4,4′-diisopropyldibenzoylmethane; 4,4′-dimethoxydibenzoylmethane;4-tert-butyl-4′-methoxydibenzoylmethane;2-methyl-5-isopropyl-4′-methoxydibenzoylmethane;2-methyl-5-tert-butyl-4′-methoxydibenzoylmethane;2,4-dimethyl-4′-methoxydibenzoylmethane;2,6-dimethyl-4-tert-butyl-4′-methoxydibenzoylmethane, and combinationsthereof.

It has been found, quite surprisingly, that substitutions on thearomatic rings at the beta positions on the acrylate moieties with anelectron donating substituent causes an increase in the polymers'ability to stabilize a photounstable compound in a composition. Withoutintending to be limited to any particular mechanism of achieving thisincrease in stability, it is believed that electron donatingsubstituents on the aryl rings increases the stability of the proposeddiradical that forms upon excitation, and thereby allows for a moreefficient kinetic dissipation of the excited state energy. Thus, thebeta positions on the acrylate moieties present in the polymersdescribed herein are preferably selected from the group consisting ofnaphthyl, phenyl, substituted naphthyl, substituted phenyl, heteroaryl,substituted heteroaryl, and combinations thereof. More preferably,selected from the group consisting of substituted naphthyl, substitutedphenyl, and substituted heteroaryl, and combinations thereof. Still morepreferably each aromatic ring contains at least one electron donatingsubstituents. Suitable electron donating substituents include, but arenot limited to alkyl, alkenyl, aryl, alkoxy, amino, alkylamino,thioether, hydroxyl, oxycarbonyl, and amido.

One embodiment of the compounds, compositions and methods describedherein is a compound of formula (I):

wherein R² is (a) phenyl substituted with 0, 1, 2, 3, or 4 R⁶substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2,3, or 4 R⁶ substituents; R¹ is selected from the group consisting ofhydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, and substituted heteroaryl; R³ and R⁴ arethe same or different and are selected from the group consisting ofC₁-C₃₀ alkyl, C₃-C₈ cycloalkyl, substituted alkyl, substitutedcycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl,substituted heteroaryl, and substituted heterocycloalkyl; X is selectedfrom the group consisting of O—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀alky-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷ is selected from the groupconsisting of hydrogen and C₁-C₂₀ alkyl; R⁵ is selected from the groupconsisting of C₃-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, substituted heteroaryl, and a structure offormula (II):

R⁹ is (a) phenyl substituted with 0, 1, 2, 3, or 4 R¹⁰ substituents or(b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R¹⁰substituents; R⁶ and R¹⁰ are the same or different and are selected fromthe group consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl,alkoxy, halo, ester, nitro, nitroso, alkylcarbonyl, alkoxycarbonyl,aryl, amino, substituted amino, amido, substituted amido, sulfate,carboxylate, oxycarbonyl, cycloalkyl, haloalkyl, cyano, and thioether;R⁸ is selected from the group consisting of hydrogen, C₂-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈ cycloalkyl, C₂-C₇heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀ substituted alkyl,C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀substituted alkynyl, C₂-C₇ substituted heterocycloalkyl, substitutedaryl, heteroaryl, and substituted heteroaryl; and n is an integer from 1to 500.

Another embodiment of a sunscreen composition disclosed herein includesa mixture of a photoactive compound and a compound of formula (I):

wherein R² is (a) phenyl substituted with 0, 1, 2, 3, or 4 R⁶substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2,3, or 4 R⁶ substituents; R¹ is hydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl,C₂-C₅₀ alkynyl, C₃-C₈ cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substituted cycloalkyl,C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇substituted heterocycloalkyl, substituted aryl, heteroaryl, orsubstituted heteroaryl; R³ and R⁴ are the same or different and areC₁-C₃₀ alkyl, C₃-C₈ cycloalkyl, substituted alkyl, substitutedcycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl,substituted heteroaryl, or substituted heterocycloalkyl; X is O—C₁-C₂₀alkyl-O—, N(R⁷)—C₁-C₂₀ alky-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷ ishydrogen or C₁-C₂₀ alkyl; R⁵ is C₃-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀alkynyl, C₃-C₈ cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substituted cycloalkyl,C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇substituted heterocycloalkyl, substituted aryl, heteroaryl, substitutedheteroaryl, or a structure of formula (II):

R⁹ is (a) phenyl substituted with 0, 1, 2, 3, or 4 R¹⁰ substituents or(b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R¹⁰substituents; R⁶ and R¹⁰ are the same or different and are hydrogen,hydroxyl, alkyl, alkenyl, alkynyl, alkoxy, halo, ester, nitro, nitroso,alkylcarbonyl, alkoxycarbonyl, aryl, amino, substituted amino, amido,substituted amido, sulfate, carboxylate, oxycarbonyl, cycloalkyl,haloalkyl, cyano, or thioether; R⁸ is hydrogen, C₂-C₅₀ alkyl, C₂-C₅₀alkenyl, C₂-C₅₀ alkynyl, C₃-C₈ cycloalkyl, C₂-C₇ heterocycloalkyl, aryl,C₁-C₅₀ polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substitutedcycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkynyl,C₂-C₇ substituted heterocycloalkyl, substituted aryl, heteroaryl, orsubstituted heteroaryl; and n is an integer from 1 to 500.

Another embodiment of the compounds, compositions, and methods describedherein is a method of protecting a surface from ultraviolet radiation,including topically applying to the surface, in a cosmeticallyacceptable carrier, a compound of formula (I):

wherein R² is (a) phenyl substituted with 0, 1, 2, 3, or 4 R⁶substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2,3, or 4 R⁶ substituents; R¹ is selected from the group consisting ofhydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, and substituted heteroaryl; R³ and R⁴ arethe same or different and are selected from the group consisting ofC₁-C₃₀ alkyl, C₃-C₈ cycloalkyl, substituted alkyl, substitutedcycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl,substituted heteroaryl, and substituted heterocycloalkyl; X is selectedfrom the group consisting of O—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀alky-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷ is selected from the groupconsisting of hydrogen and C₁-C₂₀ alkyl; R⁵ is selected from the groupconsisting of C₃-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, substituted heteroaryl, and a structure offormula (II):

R⁹ is (a) phenyl substituted with 0, 1, 2, 3, or 4 R¹⁰ substituents or(b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R¹⁰substituents; R⁶ and R¹⁰ are the same or different and are selected fromthe group consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl,alkoxy, halo, ester, nitro, nitroso, alkylcarbonyl, alkoxycarbonyl,aryl, amino, substituted amino, amido, substituted amido, sulfate,carboxylate, oxycarbonyl, cycloalkyl, haloalkyl, cyano, and thioether;R⁸ is selected from the group consisting of hydrogen, C₂-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈ cycloalkyl, C₂-C₇heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀ substituted alkyl,C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀substituted alkynyl, C₂-C₇ substituted heterocycloalkyl, substitutedaryl, heteroaryl, and substituted heteroaryl; and n is an integer from 1to 500.

As used herein, the term “cosmetically acceptable carrier” refers to acarrier which is suitable for use in contact with tissues (e.g., theskin) without undue toxicity, incompatibility, instability, irritation,allergic response, and the like.

As described above, dibenzoylmethane derivatives tend to become unstablewhen exposed to UV radiation. It has been found, quite surprisingly,that the compound described herein are capable of stabilizing adibenzoylmethane derivative present in a sunscreen composition.Accordingly, another embodiment of the compound, compositions, andmethods described herein is a method of photostabilizing adibenzoylmethane derivative, the method including the step of adding tothe dibenzoylmethane derivative a photostabilizing amount of a compoundof formula (I):

wherein R² is (a) phenyl substituted with 0, 1, 2, 3, or 4 R⁶substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2,3, or 4 R⁶ substituents; R¹ is selected from the group consisting ofhydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, and substituted heteroaryl; R³ and R⁴ arethe same or different and are selected from the group consisting ofC₁-C₃₀ alkyl, C₃-C₈ cycloalkyl, substituted alkyl, substitutedcycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl,substituted heteroaryl, and substituted heterocycloalkyl; X is selectedfrom the group consisting of O—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀alky-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷ is selected from the groupconsisting of hydrogen and C₁-C₂₀ alkyl; R⁵ is selected from the groupconsisting of C₃-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, substituted heteroaryl, and a structure offormula (II):

R⁹ is (a) phenyl substituted with 0, 1, 2, 3, or 4 R¹⁰ substituents or(b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R¹⁰substituents; R⁶ and R¹⁰ are the same or different and are selected fromthe group consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl,alkoxy, halo, ester, nitro, nitroso, alkylcarbonyl, alkoxycarbonyl,aryl, amino, substituted amino, amido, substituted amido, sulfate,carboxylate, oxycarbonyl, cycloalkyl, haloalkyl, cyano, and thioether;R⁸ is selected from the group consisting of hydrogen, C₂-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈ cycloalkyl, C₂-C₇heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀ substituted alkyl,C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀substituted alkynyl, C₂-C₇ substituted heterocycloalkyl, substitutedaryl, heteroaryl, and substituted heteroaryl; and n is an integer from 1to 500.

It has been found that the polymeric compounds described herein arecapable of accepting the triplet excited state energy of an excitedphotoactive compound. Accordingly, another embodiment of the compounds,compositions, and methods described herein is a method of quenchingtriplet excited state energy from a triplet-excited photoactive compoundin a sunscreen composition comprising adding to the composition acompound of formula (I):

wherein R² is (a) phenyl substituted with 0, 1, 2, 3, or 4 R⁶substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2,3, or 4 R⁶ substituents; R¹ is selected from the group consisting ofhydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, and substituted heteroaryl; R³ and R⁴ arethe same or different and are selected from the group consisting ofC₁-C₃₀ alkyl, C₃-C₈ cycloalkyl, substituted alkyl, substitutedcycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl,substituted heteroaryl, and substituted heterocycloalkyl; X is selectedfrom the group consisting of O—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀alky-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷ is selected from the groupconsisting of hydrogen and C₁-C₂₀ alkyl; R⁵ is selected from the groupconsisting of C₃-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, substituted heteroaryl, and a structure offormula (II):

R⁹ is (a) phenyl substituted with 0, 1, 2, 3, or 4 R¹⁰ substituents or(b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R¹⁰substituents; R⁶ and R¹⁰ are the same or different and are selected fromthe group consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl,alkoxy, halo, ester, nitro, nitroso, alkylcarbonyl, alkoxycarbonyl,aryl, amino, substituted amino, amido, substituted amido, sulfate,carboxylate, oxycarbonyl, cycloalkyl, haloalkyl, cyano, and thioether;R⁸ is selected from the group consisting of hydrogen, C₂-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈ cycloalkyl, C₂-C₇heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀ substituted alkyl,C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀substituted alkynyl, C₂-C₇ substituted heterocycloalkyl, substitutedaryl, heteroaryl, and substituted heteroaryl; and n is an integer from 1to 500.

Several methods have been used to determine the “UV-A Protective Value”of a sunscreen composition. These include the in vitro methods known as“Critical Wavelength,” “UV-A/UV-B ratio,” “UV-A Index Method” asproposed by DKG (German Society for Scientific and AppliedCosmetics)—Task Force “Sun Protection”, and the “Australian Standard” asdetermined by a “Solution” or “Thin Film Method.” They also include thein vivo methods known as “Immediate Pigment Darkening” (IPD) and“Persistent Pigment Darkening” (PPD), the latter being the methodrecommended by the Japan Cosmetic Industry Association (JCIA) and usedin Japan to measure for labeling purposes the UV-A protection efficacyof a sunscreen product. Though not officially recognized in the U.S. andEurope, the JCIA protocol is widely employed in both the U.S. and Europeto measure and compare the UV-A protective efficacy of sunscreencompositions. The UV-A Protective Value is often expressed as a value asdetermined by the particular method used. For example, UV-A ProtectiveValues are often expressed as some value “PFA,” “PA+++,” “PPD,” or“IPD.” All of these and other expressions of the UV-A Protective Valueare contemplated by the use of the term “UV-A Protective Value”throughout this disclosure. The following articles, which are all herebyincorporated herein by reference, describe these and other methods fordetermining the UV-A Protection Value: Ferrero et al., Int. J. Cosmet.Sci., 24, 63-70 (2002); Kelley et al., J. Soc. Cosmet. Chem., 44,139-151 (1993); Ming-Thau et al., J. Food & Drug Anal., 11, 128-132(2003); Heiner Gers-Barlag, The Reproducibility of an In-VitroDetermination of the UVA INDEX Describing the Relative UVA Protection ofSun Care Products, IFSCC Magazine, vol. 5, no. 3 (2002); Pissavini etal., Cosm. & Toil., 118, 63-71 (2003); “Boots of the Chemist Ltd., TheRevised Guidelines to the Practical Measurement of UVA/UVB rationsaccording to the Boots star rating system,” The Boots, Co. PLC,Nottingham, England (2004); Diffey et al., Int. J. Cosmet. Sci., 16,47-52 (1994); Wendel et al., SOFW-Journal, 127, 12-30 (2001);Gers-Barlag et al., International Sun Protection Conference, The RoyalSociety, London (2005); Dippe et al., SOFW-Journal, 131, 36-44 (2005);Refregier, International Sun Protection Conference, The Royal Society,London (2003).

It has been found, quite surprisingly, that adding a polymer terminatedwith an α-cyano β, β-diaryl acrylate derivative, such as the compoundsof formula (I) described below, increases the UV-A Protective Value. Asshown in Table III below, a sunscreen composition containing 4% byweight of Polymer Derivative 1 and 3% by weight of Avobenzone achievedan average UV-A Protection Value of 12.35 using the Persistent PigmentDarkening method (PPD), which was 3.4 times greater than the PPDstandard formulation's UV-A Protection Value on the same subjects.Accordingly, another embodiment of the compounds, compositions, andmethods described herein is a method of increasing the UV-A ProtectionValue of a sunscreen composition containing at least one photoactivecompound including the step of adding a compound of formula (I) to saidcomposition:

wherein R² is (a) phenyl substituted with 0, 1, 2, 3, or 4 R⁶substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2,3, or 4 R⁶ substituents; R¹ is selected from the group consisting ofhydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, and substituted heteroaryl; R³ and R⁴ arethe same or different and are selected from the group consisting ofC₁-C₃₀ alkyl, C₃-C₈ cycloalkyl, substituted alkyl, substitutedcycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl,substituted heteroaryl, and substituted heterocycloalkyl; X is selectedfrom the group consisting of O—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀alky-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷ is selected from the groupconsisting of hydrogen and C₁-C₂₀ alkyl; R⁵ is selected from the groupconsisting of C₃-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, substituted heteroaryl, and a structure offormula (II):

R⁹ is (a) phenyl substituted with 0, 1, 2, 3, or 4 R¹⁰ substituents or(b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R¹⁰substituents; R⁶ and R¹⁰ are the same or different and are selected fromthe group consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl,alkoxy, halo, ester, nitro, nitroso, alkylcarbonyl, alkoxycarbonyl,aryl, amino, substituted amino, amido, substituted amido, sulfate,carboxylate, oxycarbonyl, cycloalkyl, haloalkyl, cyano, and thioether;R⁸ is selected from the group consisting of hydrogen, C₂-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈ cycloalkyl, C₂-C₇heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀ substituted alkyl,C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀substituted alkynyl, C₂-C₇ substituted heterocycloalkyl, substitutedaryl, heteroaryl, and substituted heteroaryl; and n is an integer from 1to 500. Preferably, 4% by weight of a polymer terminated with an α-cyanoβ-p-methoxyphenyl β-napthyl acrylate is added to a sunscreen formulationcontaining 3% by weight of Avobenzone (i.e., a UV-A filter) and aplurality of UV-B filters. Preferably, the sunscreen compositionsdisclosed herein have a UV-A PFA value of at least about 8.0 as measuredby the JCIA “Persistent Pigment Darkening” protocol, preferably in therange of about 10 to about 15.

Compounds of formula (I) (alternatively referred to as polyesters offormula (I)) can be prepared by the transesterification of a diesterwith a diol or by the esterification of a diacid with a diol, forexample as shown below for one exemplary compound of formula (I):

Transesterification or esterification can proceed to form a polymerunder acidic, basic, or neutral conditions. When a polymer of formula(I) is prepared as shown above, the polymerization can be terminatedwith the addition of a compound, such as a alcohol, that cannot reactany further to elongate the polymer chain. The alcohol R⁵OH can beeither a cyanoacrylate or an aliphatic alcohol, or any other alcoholsuitable for reaction under the conditions necessary to form thepolyester polymer of compound (I).

EXAMPLES

The following examples are provided to illustrate the invention but arenot intended to limit the scope of the invention.

Example 1

Procedure for the synthesis of alcohol 3: Methyl2-cyano-3-(4′-methoxyphenyl)-3-(2″-naphthyl)propenoate (1 moleequivalent) is dissolved in excess of neopentyl glycol (NPG) (from 6 to8 mole equivalent) placed in 3-neck round bottom flask, and sodiumcarbonate (0.03 mole equivalent) is added. Next, the reaction mixture iscontinuously stirred and heated at 135° C. to 150° C.; throughoutreaction time, methanol is removed from the reaction mixture bycontinuous distillation applying continuous flow of nitrogen. Whenreaction is completed, typically within two hours, as monitored by gaschromatography (GC), xylenes are added to prevent solidification of thecrude product mixture, and then sodium carbonate is filtered off whilethe solution is still hot. The xylenes solution is washed several timeswith water to remove completely the excess of glycol. Xylenes are thenremoved by distillation and the product is dried under vacuum. The crudeproduct is purified by crystallization from toluene or ethyl acetate.

Synthesis of Polymer Derivative 1: Polymer Derivative 1, shown below, isprepared by combining the alcohol prepared in Example 1 with a polyesterprepared from adipic acid and neopentyl glycol.

The following procedure was used to prepare Polymer Derivative 1: Adipicacid (3 moles equivalence) and NPG glycol were placed in 3-neckround-bottom flask, assembled with column and condenser for simpledistillation to remove reaction water. The reaction mixture was thenheated at 180-200° C. until the desired acid value was achieved (aroundAV=130).

Polymer Derivative 1, a polymer of the general formula A(NA)_(n)A, (1mole equivalence; A=adipic acid and N=NPG (as shown above), NPG(2-cyano-3-(4′-methoxyphenyl)-3-(2″-naphthyl)propenoate) (1.5 moleequivalence), dibutyl ether, methane sulfonic acid catalyst (0.3% of thetotal batch weight), and an antioxidant (sodium hypophosphite; 0.03% oftotal batch weight) were placed in 3-neck round bottom flask. Thereaction flask was assembled with mechanical stirrer, thermometer andnitrogen inlet, Dean-Stark adapter, and condenser. The reaction mixturewas heated to temperature at which solvent refluxes, and the reflux wasmaintained for two hours. After two hours, 2-octyl-1-dodecanol (Isofol20) (0.3 mole equivalence) was added and the reaction was refluxed foradditional 2-4 hours. When the acid value of the reaction was less than10, the solvent was removed by distillation. Next, sodium bicarbonate(0.5% of the total batch weight) was added to the reaction vessel, andthe product was stirred for 30 minutes before filtration. The productwas filtered through filtrating aid such as Celite at highertemperature. The UV absorbance spectrum of Polymer Derivative 1 wasmeasured and is shown in FIG. 1.

Example 2

Two sunscreen compositions were prepared with the ingredients and in theamounts as indicated in Table II, and each was tested for UV absorbanceand stability:

TABLE II Polymer Polycrylene ® Derivative 1 Composition Composition IIngredient (% by weight) (% by weight) Oil Phase/UV Filters  1Polycrylene ® or Polymer 3.00 3.00 Derivative 1  2 Octisalate 5.00 5.00 3 Benzophenone-3 4.50 4.50  4 Octocrylene 2.50 2.50  5 Diethylhexyl2,6-naphthalate 2.50 2.50  6 Avobenzone 3.00 3.00  7 Steareth-21 0.600.60  8 Steareth-2 0.50 0.50  9 Cetearyl alcohol 0.35 0.35  9a Glycerylstearate & PEG-100 0.00 0.00 stearate 10 C₃₀-C₃₈ olefin/isopropyl 0.800.80 maleate/methacrylate copolymer 11 Potassium cetyl phosphate/ 3.003.00 hydrogenated palm glycerides Water Phase 12 Disodium EDTA 0.10 0.1013 Tromethamine 0.04 0.04 14 Butylene glycol 3.50 3.50 15Phenoxyethanol, Methyl 0.60 0.60 paraben, Ethyl paraben, Propyl paraben,and Isobutyl paraben Other Ingredients 16 Acrylamide/sodium 2.00 2.00acryloyldimethyltaurate copolymer/isohexadecane/ Polysorbate 80 17Methyl trimethicone 4.00 4.00 18 Dimethicone/Polysilicone-11 2.00 2.0019 Aluminum starch 2.50 2.50 octenylsuccinate 20 Water q.s. q.s.

In a vessel, ingredients 1-5 were combined, followed by the addition of6 and 7. This oil mixture was heated to about 95° C. Then, ingredients8-11 were added. In a second vessel, water (about 52.01% by weight) wasmixed with ingredient 12 until 12 dissolved. Then, 13 was added, and themixture heated to about 90° C. In a third vessel, ingredients 14 and 15were premixed and then added to the second vessel. The mixture of thefirst vessel and of the second vessel were mixed together when the firstvessel was at about 90° C. and the second vessel was at about 93° C. Theoil phase (first vessel) was added to the water phase (second vessel)with stirring and without aeration. After ten minutes, the resultingmixture was homogenized and cooled. When the mixture was at about 50°C., homogenization was stopped, and sweep mixing commenced. When themixture was at about 45° C., 16 was added. In a fourth vessel, 18 wasdiluted in 17, and when uniform, added to the mixture. Afterincorporation of the 17 and 18 mixture, ingredient 19 was added, thenwater as needed to correct for evaporative losses. Stirring wascontinued until the mixture was smooth and homogeneous.

FIGS. 1 and 2 show the photostability of a sunscreen composition thatincludes Polycrylene® (FIG. 2) and Polymer Derivative 1 (FIG. 3).Photostability is assessed by measuring the absorbance on a LabsphereUV-1000S Ultraviolet Transmittance Analyzer (softer version 1.27) beforeand after irradiation with a Solar Light Company model 16S solarsimulator (equipped with a WG 320 filter to transmit radiation greaterthan 290 nm). The radiation dose used was 35 MED. Output was monitoredby a PMA 2105 UV-B DCS Detector (biologically weighted) and controlledby a PMA 2100 Automatic Dose Controller (Solar Light Co.).

To test stability, a slide is positioned on the UV transmittanceanalyzer using registration marks, and a scan of a 1 cm spot on theslide is performed. The slide is prepared with a synthetic skinsubstrate used for testing sunscreen compositions (VITRO-SKIN substrateby IMS, Inc. of Milford, Conn.). To prepare the substrate, a 300 gsolution of 18 wt % glycerin and 82 wt % deionized water was added to ahydrating chamber (IMS), and a sheet of VITRO-SKIN was placed in thehydrating chamber and left overnight (approximately 16 hours). Several6.5 cm squares were cut from the hydrated VITRO-SKIN and these squareswere used for absorbance measurements.

To prepare the slide for testing, a minimum 100 μl of sunscreencomposition is drawn or placed into a pipette tip (Justor 1100DG, set todispense 100 μl). Using steady, even pressure on the pipette plunger,the test substance was applied to VITRO-SKIN square in a pattern of atleast 50 small dots arranged to cover a 6 cm center of a square. TheVITRO-SKIN square was then placed on a foam block, and the test materialwas spread by finger (covered with a latex glove or finger cot), firstin a circular motion, then by a side-to-side motion during which theVITRO-SKIN is deformed by the pressure. The square was then mounted in aslide holder (60 mm×60 mm glassless slide mounts with metal masks byGepe Management AG, Zug, Switzerland) and allowed to dry for 30-60minutes.

To test stability of a slide in the UV-B range, the slide was positionedon the UV transmittance analyzer using registration marks, and a scan ofa 1 cm spot on the slide was performed. The slide was then transferredto a holder placed adjacent to the solar simulator and, using acalipers, was positioned such that the beam of UV radiation exiting thesolar simulator illuminated the same 1 cm spot on the slide. To teststability of a slide in the UV-A range, a WG335 filter was installed inthe beam path. The following software settings were used: UV-B=290-320nm; UV-A=320-400 nm. Following an exposure of 35 MED for the UV-Bstudies and 120 J/cm² for the UV-A studies, the slide was again placedin position on the UV transmittance analyzer, and a scan of the exposedspot was performed.

FIG. 2 is a graph of the absorbance of the first sunscreen compositionlisted in Table II, before and after exposure to 120 J/cm² irradiation.As seen in FIG. 2, the sunscreen composition containing 3% Polycrylene®and 3% avobenzone maintained its absorbance characteristics after 120J/cm² irradiation.

FIG. 3 is a graph of the absorbance of the second sunscreen compositionlisted in Table II, before and after exposure to 120 J/cm² irradiation.As seen in FIG. 3, the sunscreen composition including 3% PolymerDerivative 1 and 3% avobenzone maintains its absorbance properties afterirradiation of 120 J/cm².

A determination of the Sun Protection Factor (SPF) of the sunscreencompositions listed in Table II was performed. To test the SPF of thecompositions, each slide is placed on the UV transmittance analyzer andscans are taken from five locations on the slide. An SPF report wasgenerated for each slide using the Labsphere software UV1000S, Version1.27. The first composition of Table II had an average SPF of 45.25,while the average SPF of the second composition of Table II (the PolymerDerivative 1 composition) was 47.94.

Example 3

Two sunscreen compositions were prepared in a similar fashion to thecompositions listed in Table II. The first, composition A, contained 4%by weight of Polymer Derivative 1, 3% by weight of Avobenzone (a U-VAfilter), and a plurality of UV-B filters. In addition, 2.5% by weight ofOctocrylene and 2.5% by weight of Diethylhexyl 2,6-naphthalate were alsoadded to composition A.

Composition B contained 3% by weight of Polycrylene®, 3% by weight ofAvobenzone (a U-VA filter), and a plurality of UV-B filters. Inaddition, 2.5% by weight of Octocrylene and 2.5% by weight ofDiethylhexyl 2,6-naphthalate were also added to composition B.

The UV-A Protection Value of the composition A was studied by thePersistent Pigment Darkening (PPD) method in accordance with theprocedures set forth by the Japan Cosmetic Industry Association. Theresults of the PPD method for composition A are shown in Table IIIbelow, wherein composition A is designated “CAB5-233”:

TABLE III APPENDIX Individual PFA Values Skin Age/ Standard SubjectCPTC# Type Sex 180 Minutes 1 I M 48458 III 35 M 3.90 2 D L 28049 III 49F 3.75 3 S C 39559 IV 37 M 4.68 4 J C 26996 III 34 M 3.75 5 M M 48425III 49 M 3.00 Average PFA (n = 5) 3.64 (95% Confidence Limits)(2.78-4.50) Standard Deviation 0.69 Standard Error 0.31 Skin Age/CAB5-233 Subject CPTC# Type Sex 180 Minutes 1 I M 48458 III 35 M 12.51 2D L 28049 III 49 F 15.63 3 S C 39559 IV 37 M 7.99 4 J C 26996 III 34 M15.63 5 M M 48425 III 49 M 10.01 Average PFA (n = 5) 12.35 (95%Confidence Limits) (8.14-16.56) Standard Deviation 3.39 Standard Error1.52As shown in Table III, composition A was tested according to the PPDprotocol on five subjects ranging in age from 35 to 49 years old. Thestandard formulation as set forth in the PPD protocol resulted in anaverage UV-Protection Value of 3.64. As determined by the PPD method,composition A had an average UV-Protection Value of 12.35, a value thatis 3.4 times that of the average measured for the standard formulationon the same subjects.

The UV-A Protection Value of Composition B was also studied by thePersistent Pigment Darkening (PPD) method in accordance with theprocedures set forth by the Japan Cosmetic Industry Association. Theresults of the PPD method for composition B are shown in Table IV below,wherein composition B is designated “CAB5-214”:

TABLE IV APPENDIX Individual PFA Values Skin Age/ Standard Subject CPTC#Type Sex 180 Minutes 1 N J 49744 IV 19 F 4.69 2 P K 20627 III 45 F 5.863 K M 12453 III 59 F 3.76 4 F L 48147 IV 34 F 3.75 5 P M 49821 III 45 M3.75 Average PFA (N = 5) 4.36 (95% Confidence Limits) (3.20-5.52)Standard Deviation 0.93 Standard Error 0.42 Skin Age/ CAB5-214 SubjectCPTC# Type Sex 180 Minutes 1 N J 49744 IV 19 F 8.76 2 P K 20627 III 45 F10.94 3 K M 12453 III 59 F 10.94 4 F L 41847 IV 34 F 10.94 5 P M 49821III 45 M 10.95 Average PFA (N = 5) 10.51 (95% Confidence Limits)(9.30-11.72) Standard Deviation 0.98 Standard Error 0.44As shown in Table IV, composition B was tested according to the PPDprotocol on five subjects ranging in age from 19 to 59 years old. Thestandard formulation as set forth in the PPD protocol resulted in anaverage UV-Protection Value of 4.36. As determined by the PPD method,composition B had an average UV-Protection Value of 10.51, a value thatis 2.4 times that of the average measured for the standard formulationon the same subjects.

These results show that the addition of a polymer terminated with aα-cyano acrylates, acrylamides, and/or thioacrylates, such as a compoundof formula (I), can substantially improve the UV-A Protection Value of asunscreen.

Example 4

A sunscreen composition was prepared with the ingredients and in theamounts indicated in Table V, and was tested for UV absorbance andstability:

TABLE V Polymer Derivative 1 Composition II Ingredient (% by weight) OilPhase/UV Filters 1 Avobenzone 3.00% 2 Oxybenzone 4.00% 3 Bemotrizinol(Tinosorb S) 0.75% 4 Octisalate 5.00% 5 Homosalate 6.50% 6 Octocrylene2.50% 7 Diethylhexyl 2,6-naphthalate 2.50% 8 Dimethyl capramide 1.00% 9Polymer Derivative 1 3.25% 10 Benzyl alcohol 0.60% 11 C₃₀₋₃₈Olefin/Isopropyl 0.80% maleate/MA copolymer 12 Cetearyl alcohol 0.35%Emulsifiers 13 Glyceryl stearate & PEG-100 2.50% stearate 14 Potassiumcetyl phosphate & 1.50% Hydrogenated palm glycerides Water Phase (w/oemulsifiers) 15 Butylene glycol 4.00% 16 Phenoxyethanol & Methyl 0.60%paraben & Ethyl paraben & Propyl paraben & Isobutyl paraben 17Triethanolamine 0.60% 18 Ensulizole (pre-neutralized with 5.00% NaOH)(15% solution) 19 Disodium EDTA 0.10% Other Ingredients 20 Carbomer(Ultrez ® 10) 0.20% 21 Acrylamide/Sodium 1.75% acryloyldimethyl tauratecopolymer & Isohexadecane & Polysorbate 80 22 Aluminum starch octenyl2.50% succinate Water 51.00%

A 500 gram batch of the formulation was made as follows: 100 grams of astock 15% solution of Ensulizole (ingredient 18) was prepared in avessel by dissolving 1.5 grams of NaOH (99%) in 82.8 grams of deionizedwater. Phenylbenzimidazole sulfonic acid (15 grams) was added to thevessel and the mixture was allowed to stir until the solution was clear.

The carbomer (ingredient 20) was pre-wetted in a second vessel by addingit to 20 grams of water and allowing it to stand for 15 minutes.Ingredients 15-17 were added to a third vessel and stirred until clearand homogeneous. In a fourth vessel, the oil phase was prepared bycombining ingredients 1-9 with stirring and heating to about 95° C.Ingredient 11-14 were added and stirred until homogeneous.

In the primary vessel, the water phase was prepared by dissolvingingredient 19 in about 250 grams of deionized water and heating thesolution to about 90° C.

Immediately before combining the oil and water phases, ingredient 10 wasadded to the oil phase with stirring. The emulsion was made by addingthe oil phase to the water phase, removing it from heat, and stirringfor 10 minutes. The emulsion was then homogenized for 10 minutes, duringwhich the pre-wetted carbomer (ingredient 20) was added. After 10minutes of homogenization, sweep stirring commenced, and when thetemperature of the batch was about 45° C., (pre-mixed) ingredients 15-17were added, followed by ingredients 18, 21, and 22. When the temperatureof the batch was about 35° C., water was added to correct forevaporative losses. Stirring continued until the mixture was smooth andhomogeneous.

FIG. 4 show the photostability of the sunscreen composition thatincludes Polymer Derivative 1 and other UV absorbing agents as listed inTable V. Photostability was assessed by measuring the absorbance on aLabsphere UV-1000S Ultraviolet Transmittance Analyzer (softer version1.27) before and after irradiation with a Solar Light Company model 16Ssolar simulator (equipped with a WG 3335 filter to transmit radiationgreater than 320 nm). The radiation dose used was 120 J/cm². Output wasmonitored by a PMA 2114 UV-A DCS Detector and controlled by a PMA 2100Automatic Dose Controller (Solar Light Co.).

To test stability, a slide is positioned on the UV transmittanceanalyzer using registration marks, and a scan of a 1 cm spot on theslide is performed. The slide is prepared with a synthetic skinsubstrate used for testing sunscreen compositions (VITRO-SKIN substrateby IMS, Inc. of Milford, Conn.). To prepare the substrate, a 300 gsolution of 18 wt % glycerin and 82 wt % deionized water was added to ahydrating chamber (IMS), and a sheet of VITRO-SKIN was placed in thehydrating chamber and left overnight (approximately 16 hours). Several6.5 cm squares were cut from the hydrated VITRO-SKIN and these squareswere used for absorbance measurements.

To prepare the slide for testing, a minimum 100 μl of sunscreencomposition is drawn or placed into a pipette tip (Justor 1100DG, set todispense 100 μl). Using steady, even pressure on the pipette plunger,the test substance was applied to VITRO-SKIN square in a pattern of atleast 50 small dots arranged to cover a 6 cm center of a square. TheVITRO-SKIN square was then placed on a foam block, and the test materialwas spread by finger (covered with a latex glove or finger cot), firstin a circular motion, then by a side-to-side motion during which theVITRO-SKIN is deformed by the pressure. The square was then mounted in aslide holder (60 mm×60 mm glassless slide mounts with metal masks byGepe Management AG, Zug, Switzerland) and allowed to dry for 30-60minutes.

To test stability of a slide in the UV-A range, a WG335 filter wasinstalled in the beam path. The following software settings were used:UV-B=290-320 nm; UV-A=320-400 nm. Following an exposure 120 J/cm² forthe UV-A studies, the slide was again placed in position on the UVtransmittance analyzer, and a scan of the exposed spot was performed.

FIG. 4 is a graph of the absorbance of the first sunscreen compositionlisted in Table V, before and after exposure to 120 J/cm² of UVradiation, 320-400 nm. As seen in FIG. 4, the sunscreen compositioncontaining 3.25% Polymer Derivative 1 maintained its absorbancecharacteristics after 120 J/cm² irradiation. This represents animprovement in photostability over the example shown in FIG. 3, whichmay be attributable to the presence of Bemotrizinol (Tinosorb S) and,perhaps, Ensulizole, in the formulation. Bemotrizinol is well-known forits photostabilizing properties.

A determination of the Sun Protection Factor (SPF) of the sunscreencomposition listed in Table V was performed. To test the SPF of thecompositions, each slide is placed on the UV transmittance analyzer andscans are taken from five locations on the slide. An SPF report wasgenerated for each slide using the Labsphere software UV1000S, Version1.27. The composition of Table V had an average SPF of 48.26.

The foregoing description is given for clearness of understanding only,and no unnecessary limitations should be understood therefrom, asmodifications within the scope of the compounds, compositions, andmethods described herein may be apparent to those having ordinary skillin the art.

1. A method of protecting a composition from ultraviolet radiation,comprising applying to said composition a compound of formula (I):

wherein R² is (a) phenyl substituted with 0, 1, 2, 3, or 4 R⁶substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2,3, or 4 R⁶ substituents; R¹ is selected from the group consisting ofaryl, and substituted aryl; R³ and R⁴ are the same or different and areselected from the group consisting of C₁-C₃₀ alkyl, C₃-C₈ cycloalkyl,substituted alkyl, substituted cycloalkyl, aryl, heteroaryl,heterocycloalkyl, substituted aryl, substituted heteroaryl, andsubstituted heterocycloalkyl; X is selected from the group consisting ofO—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀ alkyl-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷is selected from the group consisting of hydrogen and C₁-C₂₀ alkyl; R⁵is a structure of formula (II):

R⁹ is (a) phenyl substituted with 0, 1, 2, 3, or 4 R¹⁰ substituents or(b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R¹⁰substituents; R⁶ and R¹⁰ are the same or different and are selected fromthe group consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl,alkoxy, halo, ester, nitro, nitroso, alkylcarbonyl, alkoxycarbonyl,aryl, amino, substituted amino, amido, substituted amido, sulfate,carboxylate, oxycarbonyl, cycloalkyl, haloalkyl, cyano, and thioether;R⁸ is selected from the group consisting of aryl, and substituted aryl;and n is an integer from 1 to
 500. 2. The method of claim 1, wherein R¹is selected from the group consisting of naphthyl, phenyl, substitutednaphthyl, and substituted phenyl.
 3. The method of claim 1, wherein R⁶and R¹⁰ are each electron donating substituents selected from the groupconsisting of alkyl, alkenyl, aryl, alkoxy, amino, thioether, hydroxyl,oxycarbonyl, and amido.
 4. The method of claim 1, wherein R² is1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R⁶substituents.
 5. The method of claim 1, wherein R² is phenyl substitutedwith 0, 1, 2, 3, or 4 R⁶ substituents.
 6. The method of claim 1, whereinX is O—C₁-C₂₀ alkyl-O—.
 7. The method of claim 6, wherein X is selectedfrom the group consisting of


8. The method of claim 1, wherein said compound of formula (I) is:


9. A method of photostabilizing a dibenzoylmethane derivative, saidmethod comprising the step of adding to said dibenzoylmethane derivativea photostabilizing amount of a compound of formula (I):

wherein R² is (a) phenyl substituted with 0, 1, 2, 3, or 4 R⁶substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2,3, or 4 R⁶ substituents; R¹ is selected from the group consisting ofhydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, and substituted heteroaryl; R³ and R⁴ arethe same or different and are selected from the group consisting ofC₁-C₃₀ alkyl, C₃-C₈ cycloalkyl, substituted alkyl, substitutedcycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl,substituted heteroaryl, and substituted heterocycloalkyl; X is selectedfrom the group consisting of O—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀alky-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷ is selected from the groupconsisting of hydrogen and C₁-C₂₀ alkyl; R⁵ is selected from the groupconsisting of C₃-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, substituted heteroaryl, and a structure offormula (II):

R⁹ is (a) phenyl substituted with 0, 1, 2, 3, or 4 R¹⁰ substituents or(b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R¹⁰substituents; R⁶ and R¹⁰ are the same or different and are selected fromthe group consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl,alkoxy, halo, ester, nitro, nitroso, alkylcarbonyl, alkoxycarbonyl,aryl, amino, substituted amino, amido, substituted amido, sulfate,carboxylate, oxycarbonyl, cycloalkyl, haloalkyl, cyano, and thioether;R⁸ is selected from the group consisting of hydrogen, C₂-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈ cycloalkyl, C₂-C₇heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀ substituted alkyl,C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀substituted alkynyl, C₂-C₇ substituted heterocycloalkyl, substitutedaryl, heteroaryl, and substituted heteroaryl; and n is an integer from 1to
 500. 10. The method of claim 9, wherein R¹ is selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl.
 11. The method of claim 9, wherein R¹ is selected from thegroup consisting of naphthyl, phenyl, substituted naphthyl, andsubstituted phenyl.
 12. The method of claim 10, wherein said substitutedaryl and said substituted heteroaryl are substituted with an electrondonating substituent.
 13. The method of claim 12, wherein said electrondonating substituent is selected from the group consisting of alkyl,alkenyl, aryl, alkoxy, amino, alkylamino, thioether, hydroxyl,oxycarbonyl, and amido.
 14. The method of claim 9, wherein R¹ isselected from the group consisting of hydrogen, C₁-C₅₀ alkyl, and C₁-C₅₀substituted alkyl.
 15. The method of claim 9, wherein R² is 1-naphthylor 2-naphthyl substituted with 0, 1, 2, 3, or 4 R⁶ substituents.
 16. Themethod of claim 9, wherein R² is phenyl substituted with 0, 1, 2, 3, or4 R⁶ substituents.
 17. The method of claim 9, wherein R⁶ and R¹⁰ areselected from the group consisting of alkyl, alkenyl, aryl, alkoxy,amino, alkylamino, thioether, hydroxyl, oxycarbonyl, and amido.
 18. Themethod of claim 17, wherein R¹⁰ is an alkoxy substituent.
 19. The methodof claim 9, wherein X is O—C₁-C₂₀ alkyl-O—.
 20. The method of claim 19,wherein X is selected from the group consisting of


21. The method of claim 9, wherein said compound of formula (I) isselected from the group consisting of:


22. A method of quenching triplet excited state energy from atriplet-excited photoactive compound in a sunscreen compositioncomprising adding to said composition a compound of formula (I):

wherein R² is (a) phenyl substituted with 0, 1, 2, 3, or 4 R⁶substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2,3, or 4 R⁶ substituents; R¹ is selected from the group consisting ofhydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, and substituted heteroaryl; R³ and R⁴ arethe same or different and are selected from the group consisting ofC₁-C₃₀ alkyl, C₃-C₈ cycloalkyl, substituted alkyl, substitutedcycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl,substituted heteroaryl, and substituted heterocycloalkyl; X is selectedfrom the group consisting of O—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀alky-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷ is selected from the groupconsisting of hydrogen and C₁-C₂₀ alkyl; R⁵ is selected from the groupconsisting of C₃-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, substituted heteroaryl, and a structure offormula (II):

R⁹ is (a) phenyl substituted with 0, 1, 2, 3, or 4 R¹⁰ sudbstituents or(b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R¹⁰substituents; R⁶ and R¹⁰ are the same or different and are selected fromthe group consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl,alkoxy, halo, ester, nitro, nitroso, alkylcarbonyl, alkoxycarbonyl,aryl, amino, substituted amino, amido, substituted amido, sulfate,carboxylate, oxycarbonyl, cycloalkyl, haloalkyl, cyano, and thioether;R⁸ is selected from the group consisting of hydrogen, C₂-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈ cycloalkyl, C₂-C₇heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀ substituted alkyl,C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀substituted alkynyl, C₂-C₇ substituted heterocycloalkyl, substitutedaryl, heteroaryl, and substituted heteroaryl; and n is an integer from 1to
 500. 23. The method of claim 22, wherein R¹ is selected from thegroup consisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl.
 24. The method of claim 22, wherein R₁ is selected from thegroup consisting of naphthyl, phenyl, substituted naphthyl, andsubstituted phenyl.
 25. The method of claim 23, wherein said substitutedaryl and said substituted heteroaryl are substituted with an electrondonating substituent.
 26. The method of claim 25, wherein said electrondonating substituent is selected from the group consisting of alkyl,alkenyl, aryl, alkoxy, amino, alkylamino, thioether, hydroxyl,oxycarbonyl, and amido.
 27. The method of claim 22, wherein R₁ isselected from the group consisting of hydrogen, C₁-C₅₀ alkyl, and C₁-C₅₀substituted alkyl.
 28. The method of claim 22, wherein R₂ is 1-naphthylor 2-naphthyl substituted with 0, 1, 2, 3, or 4 R⁶ substituents.
 29. Themethod of claim 22, wherein R² is phenyl substituted with 0, 1, 2, 3, or4 R⁶ substituents.
 30. The method of claim 22, wherein R⁶ and R¹⁰ areselected from the group consisting of alkyl, alkenyl, aryl, alkoxy,amino, alkylamino, thioether, hydroxyl, oxycarbonyl, and amido.
 31. Themethod of claim 30, wherein R¹⁰ is an alkoxy substituent.
 32. The methodof claim 22, wherein X is O—C1-C20 alkyl-O—.
 33. The method of claim 32,wherein X is selected from the group consisting of


34. The method of claim 22, wherein said compound of formula (I) isselected from the group consisting of:


35. A method for increasing the UV-A Protection Value of a compositioncontaining at least one photoactive compound comprising adding acompound of formula (I) to said composition in an amount sufficient toincrease the UV-A Protection Value of said composition:

wherein R² is (a) phenyl substituted with 0, 1, 2, 3, or 4 R⁶substituents or (b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2,3, or 4 R⁶ substituents; R¹ is selected from the group consisting ofhydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, and substituted heteroaryl; R³ and R⁴ arethe same or different and are selected from the group consisting ofC₁-C₃₀ alkyl, C₃-C₈ cycloalkyl, substituted alkyl, substitutedcycloalkyl, aryl, heteroaryl, heterocycloalkyl, substituted aryl,substituted heteroaryl, and substituted heterocycloalkyl; X is selectedfrom the group consisting of O—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀alky-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷ is selected from the groupconsisting of hydrogen and C₁-C₂₀ alkyl; R⁵ is selected from the groupconsisting of C₃-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀substituted alkyl, C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substitutedalkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇ substituted heterocycloalkyl,substituted aryl, heteroaryl, substituted heteroaryl, and a structure offormula (II):

R⁹ is (a) phenyl substituted with 0, 1, 2, 3, or 4 R¹⁰ substituents or(b) 1-naphthyl or 2-naphthyl substituted with 0, 1, 2, 3, or 4 R¹⁰substituents; R⁶ and R¹⁰ are the same or different and are selected fromthe group consisting of hydrogen, hydroxyl, alkyl, alkenyl, alkynyl,alkoxy, halo, ester, nitro, nitroso, alkylcarbonyl, alkoxycarbonyl,aryl, amino, substituted amino, amido, substituted amido, sulfate,carboxylate, oxycarbonyl, cycloalkyl, haloalkyl, cyano, and thioether;R⁸ is selected from the group consisting of hydrogen, C₂-C₅₀ alkyl,C₂-C₅₀ alkenyl, C₂-C₅₀ alkynyl, C₃-C₈ cycloalkyl, C₂-C₇heterocycloalkyl, aryl, C₁-C₅₀ polyether, C₁-C₅₀ substituted alkyl,C₃-C₈ substituted cycloalkyl, C₂-C₅₀ substituted alkenyl, C₂-C₅₀substituted alkynyl, C₂-C₇ substituted heterocycloalkyl, substitutedaryl, heteroaryl, and substituted heteroaryl; and n is an integer from 1to
 500. 36. The method of claim 35, wherein the UV-A Protection Value ofsaid sunscreen composition is increased to about 8.0.
 37. The method ofclaim 35, wherein the UV-A Protection Value of said sunscreencomposition is increased to a value in the range of about 10.0 to about15.0.
 38. The method of claim 35, wherein said increase in UV-AProtection Value is measured according a method selected from the groupconsisting of the Critical Wavelength method, the UV-A/UV-B ratiomethod, the UV-A Index method, the Australian Standard method, theSolution method, the Thin Film method, the Immediate Pigment Darkeningmethod, and the Persistent Pigment Darkening method.
 39. The method ofclaim 35, wherein R¹ is selected from the group consisting of aryl,substituted aryl, heteroaryl, and substituted heteroaryl.
 40. The methodof claim 39, wherein R¹ is selected from the group consisting ofnaphthyl, phenyl, substituted naphthyl, and substituted phenyl.
 41. Themethod of claim 39, wherein said substituted aryl and said substitutedheteroaryl are substituted with an electron donating substituent. 42.The method of claim 41, wherein said electron donating substituent isselected from the group consisting of alkyl, alkenyl, aryl, alkoxy,amino, alkylamino, thioether, hydroxyl, oxycarbonyl, and amido.
 43. Themethod of claim 35, wherein R¹ is selected from the group consisting ofhydrogen, C₁-C₅₀ alkyl, and C₁-C₅₀ substituted alkyl.
 44. The method ofclaim 35, wherein R² is 1-naphthyl or 2-naphthyl substituted with 0, 1,2, 3, or 4 R⁶ substituents.
 45. The method of claim 35, wherein R² isphenyl substituted with 0, 1, 2, 3, or 4 R⁶ substituents.
 46. The methodof claim 35, wherein R¹⁰ is an alkoxy substituent.
 47. The method ofclaim 46, wherein R⁶ and R¹⁰ are selected from the group consisting ofalkyl, alkenyl, aryl, alkoxy, amino, alkylamino, thioether, hydroxyl,oxycarbonyl, and amido.
 48. The method of claim 35, wherein X isO—C₁-C₂₀ alkyl-O—.
 49. The method of claim 48, wherein X is selectedfrom the group consisting of


50. The method of claim 35, wherein said compound of formula (I) isselected from the group consisting of:


51. A method of photostabilizing a photoactive compound, said methodcomprising the step of adding to said photoactive compound aphotostabilizing amount of a compound of formula (III):

wherein R¹ and R⁸ are the same or different, and are selected from thegroup consisting of hydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀alkynyl, C₃-C₈ cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substituted cycloalkyl,C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇substituted heterocycloalkyl, substituted aryl, heteroaryl, andsubstituted heteroaryl; R³ and R⁴ are the same or different and areselected from the group consisting of C₁-C₃₀ alkyl, C₃-C₈ cycloalkyl,substituted alkyl, substituted cycloalkyl, aryl, heteroaryl,heterocycloalkyl, substituted aryl, substituted heteroaryl, andsubstituted heterocycloalkyl; X is selected from the group consisting ofO—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀ alkyl-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷is selected from the group consisting of hydrogen and C₁-C₂₀ alkyl; R⁹and R¹⁰ are the same or different and are each electron donating groups;and n is an integer from 1 to
 500. 52. The method of claim 51, whereinR¹ and R⁸ are the same or different and are selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl.
 53. The method of claim 52, wherein R¹ and R⁸ are the sameor different and are selected from the group consisting of phenyl, andsubstituted phenyl.
 54. The method of claim 51, wherein R¹ and R⁸ arethe same or different and are selected from the group consisting ofhydrogen, C₁-C₅₀ alkyl, and C₁-C₅₀ substituted alkyl.
 55. The method ofclaim 51, wherein R⁹ and R¹⁰ are the same or different and are selectedfrom the group consisting of alkyl, alkenyl, aryl, alkoxy, amino,alkylamino, thioether, hydroxyl, oxycarbonyl, and amido.
 56. The methodof claim 51, wherein X is O—C₁-C₂₀ alkyl-O—.
 57. The method of claim 56,wherein X is selected from the group consisting of


58. The method of claim 51, wherein said compound of formula (III) is:


59. The method of claim 51, wherein said photoactive compounds is adibenzoylmethane derivative.
 60. A sunscreen composition, comprising amixture of a photoactive compound, and a compound of formula (III):

wherein R¹ and R⁸ are the same or different and are selected from thegroup consisting of hydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀alkynyl, C₃-C₈ cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substituted cycloalkyl,C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇substituted heterocycloalkyl, substituted aryl, heteroaryl, andsubstituted heteroaryl; R³ and R⁴ are the same or different and areselected from the group consisting of C₁-C₃₀ alkyl, C₃-C₈ cycloalkyl,substituted alkyl, substituted cycloalkyl, aryl, heteroaryl,heterocycloalkyl, substituted aryl, substituted heteroaryl, andsubstituted heterocycloalkyl; X is selected from the group consisting ofO—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀ alkyl-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷is selected from the group consisting of hydrogen and C₁-C₂₀ alkyl; R⁹and R¹⁰ are the same or different and are each electron donating groups;and n is an integer from 1 to
 500. 61. The composition of claim 60,wherein R¹ and R⁸ are the same or different and are selected from thegroup consisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl.
 62. The composition of claim 61, wherein R¹ and R⁸ are thesame or different and are selected from the group consisting of phenyl,and substituted phenyl.
 63. The composition of claim 60, wherein R¹ andR⁸ are the same or different and are selected from the group consistingof hydrogen, C₁-C₅₀ alkyl, and C₁-C₅₀ substituted alkyl.
 64. Thecomposition of claim 60, wherein R⁹ and R¹⁰ are the same or differentand are selected from the group consisting of alkyl, alkenyl, aryl,alkoxy, amino, alkylamino, thioether, hydroxyl, oxycarbonyl, and amido.65. The composition of claim 60, wherein X is O—C₁-C₂₀ alkyl-O—.
 66. Thecomposition of claim 65, wherein X is selected from the group consistingof


67. The composition of claim 60, wherein said compound of formula (III)is:


68. The composition of claim 60, wherein said photoactive compounds is adibenzoylmethane derivative.
 69. A method of protecting a surface fromultraviolet radiation, comprising topically applying to said surface, ina carrier, a compound of formula (III):

wherein R¹ and R⁸ are the same or different and are selected from thegroup consisting of hydrogen, C₁-C₅₀ alkyl, C₂-C₅₀ alkenyl, C₂-C₅₀alkynyl, C₃-C₈ cycloalkyl, C₂-C₇ heterocycloalkyl, aryl, C₁-C₅₀polyether, C₁-C₅₀ substituted alkyl, C₃-C₈ substituted cycloalkyl,C₂-C₅₀ substituted alkenyl, C₂-C₅₀ substituted alkynyl, C₂-C₇substituted heterocycloalkyl, substituted aryl, heteroaryl, andsubstituted heteroaryl; R³ and R⁴ are the same or different and areselected from the group consisting of C₁-C₃₀ alkyl, C₃-C₈ cycloalkyl,substituted alkyl, substituted cycloalkyl, aryl, heteroaryl,heterocycloalkyl, substituted aryl, substituted heteroaryl, andsubstituted heterocycloalkyl; X is selected from the group consisting ofO—C₁-C₂₀ alkyl-O—, N(R⁷)—C₁-C₂₀ alkyl-N(R⁷)—, and S—C₁-C₂₀ alkyl-S—; R⁷is selected from the group consisting of hydrogen and C₁-C₂₀ alkyl; R⁹and R¹⁰ are the same or different and are each electron donating groups;and n is an integer from 1 to
 500. 70. The method of claim 69, whereinR¹ and R⁸ are the same or different and are selected from the groupconsisting of aryl, substituted aryl, heteroaryl, and substitutedheteroaryl.
 71. The method of claim 70, wherein R¹ and R⁸ are the sameor different and are selected from the group consisting of phenyl, andsubstituted phenyl.
 72. The method of claim 69, wherein R¹ and R⁸ arethe same or different and are selected from the group consisting ofhydrogen, C₁-C₅₀ alkyl, and C₁-C₅₀ substituted alkyl.
 73. The method ofclaim 69, wherein R⁹ and R¹⁰ are the same or different and are selectedfrom the group consisting of alkyl, alkenyl, aryl, alkoxy, amino,alkylamino, thioether, hydroxyl, oxycarbonyl, and amido.
 74. The methodof claim 69, wherein X is O—C₁-C₂₀ alkyl-O—.
 75. The method of claim 74,wherein X is selected from the group consisting of


76. The method of claim 69, wherein said compound of formula (III) is: